Efficient light-induced phase transitions in halogen-bonded liquid crystals
Here, we present a new family of light-responsive, fluorinated supramolecular liquid crystals (LCs) showing efficient and reversible light-induced LC-to-isotropic phase transitions. Our materials design is based on fluorinated azobenzenes, where the fluorination serves to strengthen the noncovalent interaction with bond-accepting stilbazole molecules, and increase the lifetime of the cis-form of the azobenzene units. The halogen-bonded LCs were characterized by means of X-ray diffraction, hot-stage polarized optical microscopy, and differential scanning calorimetry. Simultaneous analysis of light-induced changes in birefringence, absorption, and optical scattering allowed us to estimate tha…
Transition to Reinforced State by Percolating Domains of Intercalated Brush-Modified Cellulose Nanocrystals and Poly(butadiene) in Cross-Linked Composites Based on Thiol-ene Click Chemistry
The classic nanocomposite approach aims at percolation of low fraction of exfoliated individual reinforcing nanoscale elements within a polymeric matrix. By contrast, many of the mechanically excellent biological nanocomposites involve self-assembled and space-filled structures of hard reinforcing and soft toughening domains, with high weight fraction of reinforcements. Here we inspect a new concept toward mimicking such structures by studying whether percolation of intercalated domains consisting of alternating rigid and reinforcing, and soft rubbery domains could allow a transition to a reinforced state. Toward that, we present the functionalization of rigid native cellulose nanocrystals …
Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters : From 2D Colloidal Crystals to Spherical Capsids
We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au102-pMBA44) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template-free manner by the spontaneous patchiness of the pMBA ligands around the Au102-pMBA44 nanoclusters preferably towards equatorial plane, thus promoting inter-nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findin…
Self-organized nanostructures of poly(4-vinylpyridine), polyaniline and polyamides due to metal complexation
Comb-shaped supramolecules are constructed using flexible polymers and semi-rigid conjugated undoped or doped conjugated polymers upon complexing Zinc dodecyl benzene sulphonate, Zn(DBS) 2 . Self-organized nanostructures are formed in the bulk due to competing attractive interactions (coordination or water mediated hydrogen bonding) and repulsive polar/nonpolar interactions, showing characteristic long periods of ca. 30 A.
Generic Method for Modular Surface Modification of Cellulosic Materials in Aqueous Medium by Sequential Click-Reaction and Adsorption
A generic approach for heterogeneous surface modification of cellulosic materials in aqueous medium, applicable for a wide range of functionalizations, is presented. In the first step, carboxymethyl cellulose (CMC) modified with azide or alkyne functionality, was adsorbed on a cellulosic substrate, thus, providing reactive sites for azide–alkyne cycloaddition click reactions. In the second step, functional units with complementary click units were reacted on the cellulose surface, coated by the click-modified CMC. Selected model functionalizations on diverse cellulosic substrates are shown to demonstrate the generality of the approach. The concept by sequentially combining the robust physic…
Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology
Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB co…
Core‐Selective Silver‐Doping of Gold Nanoclusters by Surface‐Bound Sulphates on Colloidal Templates: From Synthetic Mechanism to Relaxation Dynamics
Funding Information: This work was carried out under the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), Academy of Finland's Centre of Excellence in Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland (No. 321443, 328942, 308647, and 318891) and Photonic Research and Innovation (PREIN) as well as FinnCERES flagships. L.F. and X.C. thanks for support from CSC (IT Center for Science, Finland) for providing computation resources. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/742829/EU//DRIVEN Ultra-small luminescent gold nanoclusters (AuNCs) have gained substantia…
Gold Au(I)6 Clusters with Ligand-Derived Atomic Steric Locking: Multifunctional Optoelectrical Properties and Quantum Coherence
Funding Information: This work was supported by the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), the ERC grant (834742), the EU H2020‐MSCA‐RISE‐872049 (IPN‐Bio), the Academy of Finland's Centre of Excellence in Molecular Engineering of Biosynthetic Hybrid Materials Research (HYBER, 2014–2019), and Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland project fundings (No. 352900, 314810, 333982, 336144, 352780, 352930 and 353364), FinnCERES and Photonics Research and Innovation (PREIN) flagship programs. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/834742/EU//…
Biomimetic composites with enhanced toughening using silk-inspired triblock proteins and aligned nanocellulose reinforcements
Silk-like proteins produced in bacteria are used as adhesives for cellulose nanofibrils to make a new biological material.
Highly water repellent aerogels based on cellulose stearoyl esters
Herein we combine in a novel way the physical effect of porous structure of a cellulosic aerogel with the chemical effect of long alkyl tails by a well known homogeneous green esterification method, to achieve purely bio-based and highly water repellent cellulosic materials. As an alternative for a traditional fluoro derivatized hydrophobization, here long fatty acid tails are utilized to lower the surface energy. To minimize the process emission, ionic liquid (IL) 1-allyl-3-methylimidazolium chloride is used for the esterification, due to its non-volatility and recyclability. We have shown here that low degree of substitution (DS) of the fatty acid cellulose material enables the spontaneou…
Bulk morphologies of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) triblock terpolymers
Abstract The self-assembly of block copolymers in the bulk phase enables the formation of complex nanostructures with sub 100 nm periodicities and long-range order, both relevant for nanotechnology applications. Here, we map the bulk phase behavior of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (SBT) triblock terpolymers on a series of narrowly distributed polymers with widely different block volume fractions, ϕS, ϕB and ϕT. In dependence of ϕ, we find the lamella–lamella, core-shell cylinder, cylinder-in-lamella and core-shell gyroid morphology, but also a rarely observed cylinder-in-lamella phase. The bulk morphologies are thoroughly characterized by transmission e…
Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains
Summary Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions. Here, we use halogen bonding as a supramolecular tool that directs the hierarchical self-assembly of low-molecular-weight perfluorinated molecules and diblock copolymers. Microphase separation …
Controlling Multicompartment Morphologies Using Solvent Conditions and Chemical Modification
The solution self-assembly of amphiphilic diblock copolymers into spheres, cylinders, and vesicles (polymersomes) has been intensely studied over the past two decades, and their morphological behavior is well understood. Linear ABC triblock terpolymers with two insoluble blocks A/B, on the other hand, display a richer and more complex morphological spectrum that has been recently explored by synthetic block length variations. Here, we describe facile postpolymerization routes to tailor ABC triblock terpolymer solution morphologies by altering block solubility (solvent mixtures), blending with homopolymers, and block-selective chemical reactions. The feasibility of these processes is demonst…
Reversible Supracolloidal Self-Assembly of Cobalt Nanoparticles to Hollow Capsids and Their Superstructures
| openaire: EC/FP7/291364/EU//MIMEFUN The synthesis and spontaneous, reversible supracolloidal hydrogen bond-driven self-assembly of cobalt nanoparticles (CoNPs) into hollow shell-like capsids and their directed assembly to higher order superstructures is presented. CoNPs and capsids form in one step upon mixing dicobalt octacarbonyl (Co2CO8) and p-aminobenzoic acid (pABA) in 1,2-dichlorobenzene using heating-up synthesis without additional catalysts or stabilizers. This leads to pABA capped CoNPs (core ca. 5nm) with a narrow size distribution. They spontaneously assemble into tunable spherical capsids (d≈50-200nm) with a few-layered shells, as driven by inter-nanoparticle hydrogen bonds th…
CCDC 1449804: Experimental Crystal Structure Determination
Related Article: Francisco Fernandez-Palacio, Mikko Poutanen, Marco Saccone, Antti Siiskonen, Giancarlo Terraneo, Giuseppe Resnati, Olli Ikkala, Pierangelo Metrangolo, and Arri Priimagi|2016|Chem.Mater.|28|8314|doi:10.1021/acs.chemmater.6b03460
CCDC 1449805: Experimental Crystal Structure Determination
Related Article: Francisco Fernandez-Palacio, Mikko Poutanen, Marco Saccone, Antti Siiskonen, Giancarlo Terraneo, Giuseppe Resnati, Olli Ikkala, Pierangelo Metrangolo, and Arri Priimagi|2016|Chem.Mater.|28|8314|doi:10.1021/acs.chemmater.6b03460
CCDC 1449802: Experimental Crystal Structure Determination
Related Article: Francisco Fernandez-Palacio, Mikko Poutanen, Marco Saccone, Antti Siiskonen, Giancarlo Terraneo, Giuseppe Resnati, Olli Ikkala, Pierangelo Metrangolo, and Arri Priimagi|2016|Chem.Mater.|28|8314|doi:10.1021/acs.chemmater.6b03460